Application of Assembly-line Synthesis to Conformationally Designed Cyclic and Acyclic Molecules

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This project describes the application of assembly-line synthesis to cyclic and acyclic molecules with designed conformation and the detailed investigation of the substituent effects on the shape of those molecules. Aggarwal's assembly-line synthesis is a unique method that allows to grow a carbon chain by iterative homologation of boronic esters using chiral lithiated carbamates or esters as building blocks. This method works with high fidelity and does not require purification of intermediates. Although conformational control of a long alkyl chain depending on the configuration and position of substituents represents a challenging task, initial experiments demonstrated that control of the overall shape (e.g. the degree of helicity) can be achieved. In this project, the extent of conformational control as a function of the distance from the main chain will be explored in more complex systems. Furthermore, limits of the conformational control by substituents will be studied. This will provide an opportunity for the precise relative positioning of molecular fragments of variable size. A better understanding of conformational control will pave the way to the rational design of molecules with unprecedented shape-specificity which could e.g. be capable of binding to protein surfaces in a highly selective manner.